Fungicide hydroximoyl-tetrazole derivatives

ABSTRACT

The present invention relates to hydroximoyl-tetrazole derivatives of formula (I) wherein T represent a tetrazolyl substituent, A represents a carbo- or heterocycle, L 1  and L 2  represent various linking groups and Q represents a 5-membered heterocycle, their process of preparation, their use as fungicide active agents, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

The present invention relates to hydroximoyl-tetrazoles derivatives, their process of preparation, their use as fungicide active agents, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

In European patent application no. 1426371, there are disclosed certain tetrazoyloxime derivatives of the following chemical structure:

wherein A represents a tetrazolyl group, Het represents either a particular pyridinyl group or a particular thiazolyl group.

In Japanese patent application no. 2004-131392, there are disclosed certain tetrazoyloxime derivatives of the following chemical structure:

wherein Q can be selected in a list of 15 various heterocycle groups.

In Japanese patent application no. 2004-131416, there are disclosed certain tetrazoyloxime derivatives of the following chemical structure:

wherein Q can be selected among a pyridinyl group or a thiazolyl group.

The compounds disclosed in these three documents do not prove to provide a comparable utility than the compounds according to the invention.

It is always of high-interest in agriculture to use novel pesticide compounds in order to avoid or to control the development of resistant strains to the active ingredients. It is also of high-interest to use novel compounds being more active than those already known, with the aim of decreasing the amounts of active compound to be used, whilst at the same time maintaining effectiveness at least equivalent to the already known compounds. We have now found a new family of compounds which possess the above mentioned effects or advantages.

Accordingly, the present invention provides hydroximoyl-tetrazole derivatives of formula (I)

wherein

-   -   T represents a substituted or non-substituted tetrazolyl group;     -   L¹ represents a direct bond or a divalent group selected in the         list consisting of         -   —(CR¹R²)_(n)— —(CR¹R²)_(m)—C(═O)—(CR¹R²)_(p)—         -   —(CR¹R²)_(m)—(CR¹═CR²)—(CR¹R²)_(p)—             —(CR¹R²)_(m)—C(═O)—(CR¹R²)_(p)         -   —(CR¹R²)_(m)—C≡C—(CR¹R²)_(p)— —(CR¹R²)_(m)—O—C(═O)—(CR¹R²)—         -   —(CR¹R²)_(m)—O—(CR¹R²)_(p)—             —(CR¹R²)_(m)—C(═O)—NH—(CR¹R²)_(p)—         -   —(CR¹R²)_(m)—NH—(CR¹R²)_(p)—             —(CR¹R²)_(m)—NH—C(═O)—(CR¹R²)_(p)—             wherein     -   n represents 1, 2, 3 or 4;     -   m and p independently represent 0, 1, 2 or 3;     -   L² represents a direct bond or a divalent group selected in the         list consisting of         -   —(CR³R⁴)_(q)— —(CR³R⁴)_(a)—C(═O)—(CR³R⁴)_(b)—         -   —(CR³R⁴)_(a)—(CR³═CR⁴)—(CR³R⁴)_(b)—             —(CR³R⁴)_(a)—C(═O)—O—(CR³R⁴)_(b)         -   —(CR³R⁴)_(a)—C≡C—(CR³R⁴)_(b)—             —(CR³R⁴)_(a)—O—C(═O)—(CR³R⁴)_(b)—         -   —(CR³R⁴)_(a)—O—(CR³R⁴)_(b)—             —(CR³R⁴)_(a)—C(═O)—NH—(CR³R⁴)_(b)—         -   —(CR³R⁴)_(a)—NH—(CR³R⁴)_(b)—             —(CR³R⁴)_(a)—NH—C(═O)—(CR³R⁴)_(b)—             wherein     -   q represents 1, 2, 3 or 4;     -   a and b independently represent 0, 1, 2 or 3;     -   A is selected in the list consisting of A¹ to A¹¹⁶

wherein

-   -   Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected         in the list consisting of hydrogen, halogen, [C₁-C₈]-alkyl,         [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl,         [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl,         [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl,         hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁵,         —C(═O)OR⁵, —C(═O)NR⁵R⁶, —C(═O)SR⁵, —C(═S)R⁵, —C(═S)OR⁵,         —C(═S)NR⁵R⁶, —C(═S)SR⁵, —CR⁵═NR⁶, —CR⁵═NOR⁶, —CR⁵═N—NR⁶R⁷, —OR⁵,         —OSiR⁵R⁶R⁷, —OC(═O)R⁵—OC(═O)OR⁵, OC(═O)NR⁵R⁶, —OC(═S)NR⁵R⁶,         —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, N(R⁵)C(═O)NR⁶R⁷,         —N(R⁵)C(═S)R⁶, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶,         —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)OR⁶, —N(R⁵)NR⁶R⁷, —N═NR⁵,         —N(R⁵)S(═O)R⁶, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)OR⁶,         —N(R⁵)S(═O)NR⁶R⁷, —N(R⁵)S(═O)₂NR⁶R⁷, —SR⁵, —S(═O)R⁵, —S(═O)₂R⁵,         —S(═O)OR⁵, —S(═O)NR⁵R⁶, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶, nitro,         nitroso, azido, cyano, —SF₅ and —SiR⁵R⁶R⁷;     -   K¹ and K² are independently selected in the list consisting of         hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl,         aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl,         [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁹, —C(═O)OR⁹, —C(═O)NR⁹R¹⁰,         —C(═O)SR⁹, —C(═S)R⁹, —C(═S)OR⁹, —C(═S)NR⁹R¹⁰, —C(═S)SR⁹,         —CR⁹═NR¹⁰, —CR⁹═NOR¹⁰, —CR⁹═N—NR¹⁰R¹¹, —S(═O)R⁹, —S(═O)₂R⁹,         —S(═O)OR⁹, —S(═O)NR⁹R¹⁰, —S(═O)₂OR⁹, —S(═O)₂NR⁹R¹⁰ and         —SiR⁹R¹⁰R¹¹;     -   G¹ and G² are independently selected in the list consisting of         oxygen, sulfur, NR¹², N—OR¹² and N—NR¹²R¹³;     -   Q is selected in the list consisting of Q¹ to Q⁷²

wherein

-   -   X¹, X², X³, X⁴ and X⁵ are independently selected in the list         consisting of hydrogen, halogen, [C₁-C₈]-alkyl,         [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl,         [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl,         [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl,         hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R¹⁴,         —C(═O)OR¹⁴, —C(═O)NR¹⁴R¹⁵, —C(═O)SR¹⁴, —C(═S)R¹⁴, —C(═S)OR¹⁴,         —C(═S)NR¹⁴R¹⁵, —C(═S)SR¹⁴, —CR¹⁴═NR¹⁵, —CR¹⁴═NOR¹⁵,         —CR¹⁴═N—NR¹⁵R¹⁶, —OR¹⁴, —OSiR¹⁴R¹⁵R¹⁶, —OC(═O)R¹⁴—OC(═O)OR¹⁴,         —OC(═O)NR¹⁴R¹⁵, —OC(═S)NR¹⁴R¹⁵, —NR¹⁴R¹⁵, —N(R¹⁴)C(═O)R¹⁵,         —N(R¹⁴)C(═O)OR¹⁵—N(R¹⁴)C(═O)NR¹⁵R¹⁶, —N(R¹⁴)C(═S)R¹⁵,         —N(R¹⁴)C(═S)NR¹⁵R¹⁶, —N═CR¹⁴R¹⁵, —N═C—NR¹⁴R¹⁵,         —N(R¹⁴)C(═NR¹⁵)NR¹⁶R¹⁷, —N(R¹⁴)OR¹⁵, —N(R¹⁴)NR¹⁵R¹⁶, —N═NR¹⁴,         —N(R¹⁴)S(═O)R¹⁵, —N(R¹⁴)S(═O)₂R¹⁵, —N(R¹⁴)S(═O)₂OR¹⁵,         —N(R¹⁴)S(═O)OR¹⁵, —N(R¹⁴)S(═O)NR¹⁵R¹⁶, —N(R¹⁴)S(═O)₂NR¹⁵R¹⁶,         —SR¹⁴, —S(═O)R¹⁴, —S(═O)₂R¹⁴, —S(═O)OR¹⁴, —S(═O)NR¹⁴R¹⁵,         —S(═O)₂OR¹⁴, —S(═O)₂NR¹⁴R¹⁵, nitro, nitroso, azido, cyano, —SF₅         and —SiR¹⁴R¹⁵R¹⁶;     -   W¹ is selected in the list consisting of hydrogen,         [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl,         aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl,         [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁹, —C(═O)OR⁹, —C(═O)NR⁹R¹⁰,         —C(═O)SR⁹, —C(═S)R⁹, —C(═S)OR⁹, —C(═S)NR⁹R¹⁰, —C(═S)SR⁹,         —CR⁹═NR¹⁰, —CR⁹═NOR¹⁰, —CR⁹═N—NR¹⁰R¹¹, —S(═O)R⁹, —S(═O)₂R⁹,         —S(═O)OR⁹, —S(═O)NR⁹R¹⁰, —S(═O)OR⁹, —S(═O)NR⁹R¹⁰ and         —SiR⁹R¹⁰R¹¹;     -   R¹, R², R³ and R⁴ are independently selected in the list         consisting of hydrogen, halogen, [C₁-C₄]-alkyl,         [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl,         [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl,         [C₃-C₅]-halocycloalkyl, [C₁-C₄]-alkoxy,         [C₁-C₄]-alkoxy-[C₁-C₄]-alkyl, [C₁-C₄]-alkoxy-[C₁-C₄]-alkoxy,         [C₁-C₄]-haloalkoxy, [C₁-C₄]-haloalkoxy-[C₁-C₄]-alkyl and cyano;     -   R⁵ to R¹⁷ are independently selected in the list consisting of         hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl and         aryl-[C₁-C₈]-alkyl;         as well as salts, N-oxides, metallic complexes and metalloidic         complexes thereof.

Any of the compounds according to the invention can exist as one or more stereoisomers depending on the number of stereogenic units (as defined by the IUPAC rules) in the compound. The invention thus relates equally to all the stereoisomers, and to the mixtures of all the possible stereoisomers, in all proportions. The stereoisomers can be separated according to the methods which are known per se by the man ordinary skilled in the art. According to the invention, the following generic terms are generally used with the following meanings:

-   -   halogen means fluorine, chlorine, bromine or iodine;     -   heteroatom can be nitrogen, oxygen or sulphur;     -   halogenated groups, notably haloalkyl, haloalkoxy and cycloalkyl         groups, may comprise up to nine identical or different halogen         atoms;     -   the term “aryl” means phenyl or naphthyl, optionally substituted         by one to five groups selected in the list consisting of         halogen, [C₁-C₆]-alkyl, [C₁-C₆]-haloalkyl, [C₂-C₆]-alkenyl,         [C₂-C₆]-haloalkenyl, [C₂-C₆]-alkynyl, [C₂-C₆]-haloalkynyl,         [C₁-C₆]-alkoxy, [C₁-C₄]-alkoxy-[C₁-C₄]-alkyl,         [C₁-C₄]-alkoxy-[C₁-C₄]-alkoxy, [C₁-C₆]-haloalkoxy and         [C₁-C₄]-haloalkoxy-[C₁-C₄]-alkyl.

As a further aspect, the present invention provides hydroximoyl-tetrazole derivatives of formula (Ia), (Ib), (Ic) and (Id)

wherein

-   -   A, Q, L¹ and L² are defined in the same manner as the         corresponding substituents of the compounds of formula (I)         according to the invention;     -   E¹ is selected in the list consisting of hydrogen,         [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl,         aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl,         [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸,         —C(═O)NR¹⁸R¹⁹, —C(═O)SR¹⁸, —C(═S)R¹⁸, —C(═S)OR¹⁸, —C(═S)NR¹⁸R¹⁹,         —C(═S)SR¹⁸, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)R¹⁸,         —S(═O)₂R¹⁸, —S(═O)OR¹⁸, —S(═O)NR¹⁸R¹⁹, —S(═O)₂OR¹⁸,         —S(═O)₂NR¹⁸R¹⁹, cyano, and —SiR¹⁸R¹⁹R²⁰;     -   E² is selected in the list consisting of hydrogen, halogen,         [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl,         aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl,         [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸,         —C(═O)NR¹⁸R¹⁹, —C(═O)SR¹⁸, —C(═S)R¹⁸, —C(═S)OR¹⁸, —C(═S)NR¹⁸R¹⁹,         —C(═S)SR¹⁸, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸,         —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)OR¹⁸, —OC(═O)NR¹⁸R¹⁹,         —OC(═S)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹,         —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰,         —N═CR¹⁸R¹⁹, —N═C—NR¹⁸R¹⁹, —N(R¹⁸)C(═NR¹⁹)NR²⁰R²¹, —N(R¹⁸)OR¹⁹,         —N(R¹⁸)NR¹⁹R²⁰, —N═NR¹⁸, —N(R¹⁸)S(═O)R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹,         —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)OR¹⁹, —N(R¹⁸)S(═O)NR¹⁹R²⁰,         —N(R¹⁸)S(═O)₂NR¹⁹R²⁰, —SR¹⁸, —S(═O)R¹⁹, —S(═O)₂R¹⁸, —S(═O)OR¹⁸,         —S(═O)NR¹⁸R¹⁹, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano, —SF₅ and         —SiR¹⁸R¹⁹R²⁰;     -   R¹⁸ to R²⁰ are independently selected in the list consisting of         hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl,         [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl,         [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl and         aryl-[C₁-C₈]-alkyl.

Preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein L¹ represents a direct bond or a divalent group selected in the list consisting of

-   -   —(CR¹R²)_(n)— —C(═O)—(CR¹R²)_(p)—     -   —(CR¹R²)_(m)—O— 13 (CR¹R²)_(m)—C(═O)—O—     -   —(CR¹R²)_(m)—NH— —(CR¹R²)_(m)—C(═O)NH—     -   —(CR¹R²)_(m)—C(═O)— —(CR¹R²)_(m)—NH—C(═O)         wherein     -   n represents 1 or 2;     -   m and p independently represent 0 or 1;     -   R¹ and R² are independently selected in the list consisting of         hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl,         [C₂-C₄]-alkenyl, [C₂-C₄]-alkynyl, [C₃-C₅]-cycloalkyl,         [C₁-C₄]-alkoxy, [C₁-C₄]-haloalkoxy and cyano.

More preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein L¹ represents a direct bond or a divalent group selected in the list consisting of —(CR¹R²)—, —C(═O)—(CR¹R²)— and —C(═O)—; wherein R¹ and R² are independently selected in the list consisting of hydrogen, halogen, methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy and cyano.

Other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein L² represents a direct bond or a divalent group selected in the list consisting of

-   -   —(CR³R⁴)_(q)— —(CR³R⁴)_(a)—C(═O)—     -   —(CR³═CR⁴)— —(CR³R⁴)_(a)—C(═O)—O—     -   —C≡C— —(CR³R⁴)_(a)—O—C(═O)—     -   —(CR³R⁴)_(a)—O— —(CR³R⁴)_(a)—C(═O)NH—     -   —(CR³R⁴)_(a)—NH— —(CR³R⁴)_(a)—NH—C(═O)—         wherein     -   q and a independently represent 1 or 2;     -   R³ and R⁴ are independently selected in the list consisting of         hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl,         [C₂-C₄]-alkenyl, [C₂-C₄]-alkynyl, [C₃-C₅]-cycloalkyl,         [C₁-C₄]-alkoxy, [C₁-C₄]-haloalkoxy and cyano.

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein L² represents a direct bond or —(CR³R⁴)— wherein R³ and R⁴ are independently selected in the list consisting of hydrogen, halogen, methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy and cyano.

Still other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein A is selected in the list consisting of A¹ to A³².

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein A is selected in the list consisting of A², A⁶, A⁸, A¹⁵, A¹⁶, A¹⁷ and A¹⁸.

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Z¹ is selected in the list consisting of hydrogen, —C(═O)R⁵, —C(═O)OR⁵, —C(═O)NR⁵R⁶, —C(═S)NR⁵R⁶, —CR⁵═NR⁶, —CR⁵═NOR⁶, —CR⁵═N—NR⁶R⁷, —OR⁵, —OC(═O)R⁵, —OC(═O)OR⁵, —OC(═O)NR⁵R⁶, —OC(—S)NR⁵R⁶, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, —N(R⁵)C(═O)NR⁶R⁷, —N(R⁵)C(═S)R⁶, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶, —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)OR⁶, —N(R⁵)NR⁶R⁷, —N═NR⁵, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)₂NR⁶R⁷, —SR⁵, —S(═O)₂R⁵, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶ and cyano.

Other even more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Z¹ is selected in the list consisting of hydrogen, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, —N(R⁵)C(═O)NR⁶R⁷, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶, —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)₂NR⁶R⁷ and cyano.

Still other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, —C(═O)R⁵, —C(═O)OR⁵, —C(═O)NR⁵R⁶, —OR⁵, —OSiR⁵R⁶R⁷, —OC(═O)R⁵, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —SR⁵, —S(═O)₂R⁵, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶, cyano and —SiR⁵R⁶R⁷; wherein R⁵, R⁶, and R⁷ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl and [C₃-C₅]-cycloalkyl.

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, methyl, ethyl, iso-propyl, iso-butyl, tert-butyl, [C₁-C₄]-haloalkyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy, acetyl, trifluoroacetyl and cyano.

Still other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein K¹, K² and W¹ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, methyl, ethyl, iso-propyl, iso-butyl, tert-butyl, allyl, propargyl, cyclopropyl, acetyl, trifluoroacetyl and mesyl.

Still other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Q is selected in the list consisting of Q¹ to Q²⁶.

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein Q is selected in the list consisting of Q³, Q⁴, Q⁶, Q⁷, Q⁹, Q¹² and Q¹⁵.

Still other preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein X¹ to X⁵ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, aryl, aryl-[C₁-C₂]-alkyl, —C(═O)R¹⁴, —C(═O)OR¹⁴, —C(═O)NR¹⁴R¹⁵, —CR¹⁴═NOR¹⁵, —CR¹⁴═N—NR¹⁵R¹⁶, —OR¹⁴, —OSiR¹⁴R¹⁵R¹⁶, —OC(═O)R¹⁴, —OC(═O)OR¹⁴, —OC(═O)NR¹⁴R¹⁵, —NR¹⁴R¹⁵, —N(R¹⁴)C(═O)R¹⁵, —SR¹⁴, —S(═O)₂R¹⁴, —S(═O)₂OR¹⁴, —S(═O)₂NR¹⁴R¹⁵, cyano and —SiR¹⁴R¹⁵R¹⁶; wherein R¹⁴, R¹⁵, and R¹⁶ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl and [C₃-C₅]-cycloalkyl, aryl and aryl-[C₁-C₂]-alkyl.

Other more preferred compounds of formula (I) and (Ia) to (Id) according to the invention are those wherein X¹ to X⁵ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, methyl, iso-propyl, iso-butyl, tert-butyl, [C₁-C₄]-haloalkyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, benzyl, phenethyl, methoxy, trifluoromethoxy, acetyl, trifluoroacetyl and cyano.

Preferred compounds of formula (Ia) to (Id) according to the invention are those wherein E¹ is selected in the list consisting of [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl and cyclopropyl.

More preferred compounds of formula (Ia) to (Id) according to the invention are those wherein E¹ is selected in the list consisting of methyl, ethyl, iso-propyl, allyl, propargyl, cyclopropyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹ and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of methyl and trifluoromethyl.

Other preferred compounds of formula (Ia) to (Id) according to the invention are those wherein E² is selected in the list consisting of halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸, —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)R¹⁸, —OC(═O)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹, —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰, —N═CR¹⁸R¹⁹, —N═C—NR¹³R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹, —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)NR¹⁹R²⁰, —SR¹⁸, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl and [C₁-C₄]-haloalkyl.

Other more preferred compounds of formula (Ia) to (Id) according to the invention are those wherein E² is selected in the list consisting of methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, cyano, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸, —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)OR¹⁸, —OC(═O)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹, —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰, —N═CR¹⁸R¹⁹, —N═C—NR¹⁸R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹, —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)₂NR¹⁹R²⁰, —SR¹⁸, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹ and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, methyl and trifluoromethyl.

The above mentioned preferences with regard to the substituents of the compounds of formula (I) and (Ia) to (Id) according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention can combine:

-   -   preferred features of A with preferred features of one or more         of L¹, L², Q, E¹ and E²;     -   preferred features of L¹ with preferred features of one or more         of A, L², Q, E¹ and E²;     -   preferred features of L² with preferred features of one or more         of A, L¹, Q, E¹ and E²;     -   preferred features of Q with preferred features of one or more         of A, L¹, L², E¹ and E²;     -   preferred features of E¹ with preferred features of one or more         of A, L¹, L², Q and E²;     -   preferred features of E² with preferred features of one or more         of A, L¹, L², Q and E¹.

In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of A, Q, L¹, L², E¹ and E²; so as to form most preferred subclasses of compounds according to the invention.

The preferred features of the other substituents of the compounds according to the invention can also be part of such sub-classes of preferred compounds according to the invention, notably the groups of substituents R, Z, K, G, X and W as well as the integers a, b, m, n, p and q.

The present invention also relates to a process for the preparation of compounds of formula (I), (Ia), (Ib), (Ic) and (Id). Thus, according to a further aspect of the present invention, there is a provided process P1 for the preparation of compounds of formula (I), (Ia), (Ib), (Ic) and (Id) as herein-defined, as illustrated by the following reaction schemes.

wherein A, L¹, L², Q, E¹ and E² are as herein-defined and LG represents a leaving group. Suitable leaving groups can be selected in the list consisting of a halogen atom or other customary nucleofugal groups such as triflate, mesylate, or tosylate.

For the compounds of formula (I) according to the invention when Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ or Z⁹ represents an amino group, process P1 according to the invention can be completed by a further step comprising the additional modification of this group, notably by a reaction of acylation, alkoxycarbonylation, alkylaminocarbonylation or alkylaminothiocarbonylation, according to known methods. In such a case there is provided a process P2 according to the invention and such a process P2 can be illustrated by the following reaction schemes:

wherein A, L¹, L², T, Q and R⁵ are as herein-defined.

If Z¹, Z², Z³, Z⁴ Z⁵, Z⁶, Z⁷, Z⁸ or Z⁹ represents a protected amino group, carrying out process P2 would previously require a deprotection step in order to yield the amino group. Amino-protecting groups and related methods of cleavage thereof are known and can be found in T. W. Greene and P. G. M. Wuts, Protective Group in Organic Chemistry, 3^(rd) ed., John Wiley & Sons.

According to the invention, processes P1 and P2 may be performed if appropriate in the presence of a solvent and if appropriate in the presence of a base.

Suitable solvents for carrying out processes P1 and P2 according to the invention are customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n- or iso-butyronitrile or benzonitrile; amides, such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, or sulphones, such as sulpholane.

Suitable bases for carrying out processes P1 and P2 according to the invention are inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate, and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethylaminopyridine, 1,4-diazabicyclo[2.2.2]octane (DABCO), 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diaza-bicyclo[5.4.0]undec-7-ene (DBU).

When carrying out processes P1 and P2 according to the invention, the reaction temperature can independently be varied within a relatively wide range. Generally, process P1 according to the invention is carried out at temperatures between 0° C. and 160° C.

Processes P1 and P2 according to the invention are generally independently carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.

When carrying out process P1 according to the invention, generally 1 mol or an excess of derivative of formula A-L¹-LG and from 1 to 3 mol of base are employed per mole of hydroximoyl tetrazoles of formula (IVa), (IVb), (Va) or (Vb). It is also possible to employ the reaction components in other ratios.

Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that may still be present.

Compounds according to the invention can be prepared according to the above described processes. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt these processes according to the specifics of each of the compounds according to the invention that is desired to be synthesised.

The compounds of formula (IVa) and (IVb), useful as a starting material, can be prepared, for example, by reacting hydroxylamine with the corresponding ketones that can be prepared, for example, according to the method described by R. Raap (Can. J. Chem. 1971, 49, 2139) by addition of a tetrazolyl lithium species to esters of formula Q-L²-CO₂Me or Q-L²-CO₂Et, or any of their suitable synthetic equivalents like, for example: Q-L²-C(═O)—N(OMe)Me, Q-L²-CN, Q-L²-C(═O)Cl.

The compounds of general formula (Va) and (Vb), useful as a starting material, can be prepared, for example, from oximes of formula Q-L²-CH═N—OH and 5-substituted tetrazoles according to the method described by J. Plenkiewicz et al. (Bull. Soc. Chim. Belg. 1987, 96, 675).

In a further aspect, the present invention also relates to a fungicide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I) or (Ia) to (Id).

The expression “effective and non-phytotoxic amount” means an amount of composition according to the invention which is sufficient to control or destroy the fungi present or liable to appear on the crops, and which does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.

Thus, according to the invention, there is provided a fungicide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) or (Ia) to (Id) as herein defined and an agriculturally acceptable support, carrier or filler.

According to the invention, the term “support” denotes a natural or synthetic, organic or inorganic compound with which the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support may be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol, organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports may also be used.

The composition according to the invention may also comprise additional components. In particular, the composition may further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention may be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols, and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water. Preferably, surfactant content may be comprised from 5% to 40% by weight of the composition.

Optionally, additional components may also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, which complies with the usual formulation techniques.

In general, the composition according to the invention may contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.

Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure), gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions which must be diluted before application to the crop.

The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous.

Examples of suitable fungicide mixing partners may be selected in the following lists

-   -   B1) a compound capable to inhibit the nucleic acid synthesis         like benalaxyl, benalaxyl-M, bupirimate, clozylacon,         dimethirimol, ethirimol, furalaxyl, hymexazol, mefenoxam,         metalaxyl, metalaxyl-M, ofurace, oxadixyl, oxolinic acid;     -   B2) a compound capable to inhibit the mitosis and cell division         like benomyl, carbendazim, diethofencarb, ethaboxam,         fuberidazole, pencycuron, thiabendazole, thiophanate-methyl,         zoxamide;     -   B3) a compound capable to inhibit the respiration for example         -   as CI-respiration inhibitor like diflumetorim;         -   as CII-respiration inhibitor like boscalid, carboxin,             fenfuram, flutolanil, furametpyr, furmecyclox, mepronil,             oxycarboxin, penthiopyrad, thifluzamide;         -   as CIII-respiration inhibitor like amisulbrom, azoxystrobin,             cyazofamid, dimoxystrobin, enestrobin, famoxadone,             fenamidone, fluoxastrobin, kresoxim-methyl, metominostrobin,             orysastrobin, picoxystrobin, pyraclostrobin,             trifloxystrobin;     -   B4) a compound capable of to act as an uncoupler like dinocap,         fluazinam, meptyldinocap;     -   B5) a compound capable to inhibit ATP production like fentin         acetate, fentin chloride, fentin hydroxide, silthiofam;     -   B6) a compound capable to inhibit AA and protein biosynthesis         like andoprim, blasticidin-S, cyprodinil, kasugamycin,         kasugamycin hydrochloride hydrate, mepanipyrim, pyrimethanil;     -   B7) a compound capable to inhibit the signal transduction like         fenpiclonil, fludioxonil, quinoxyfen;     -   B8) a compound capable to inhibit lipid and membrane synthesis         like biphenyl, chlozolinate, edifenphos, etridiazole, iodocarb,         iprobenfos, iprodione, isoprothiolane, procymidone, propamocarb,         propamocarb hydrochloride, pyrazophos, tolclofos-methyl,         vinclozolin;     -   B9) a compound capable to inhibit ergosterol biosynthesis like         aldimorph, azaconazole, bitertanol, bromuconazole,         cyproconazole, diclobutrazole, difenoconazole, diniconazole,         diniconazole-M, dodemorph, dodemorph acetate, epoxiconazole,         etaconazole, fenarimol, fenbuconazole, fenhexamid, fenpropidin,         fenpropimorph, fluquinconazole, flurprimidol, flusilazole,         flutriafol, furconazole, furconazole-cis, hexaconazole,         imazalil, imazalil sulfate, imibenconazole, ipconazole,         metconazole, myclobutanil, naftifine, nuarimol, oxpoconazole,         paclobutrazol, pefurazoate, penconazole, prochloraz,         propiconazole, prothioconazole, pyributicarb, pyrifenox,         simeconazole, spiroxamine, tebuconazole, terbinafine,         tetraconazole, triadimefon, triadimenol, tridemorph,         triflumizole, triforine, triticonazole, uniconazole,         viniconazole, voriconazole;     -   B10) a compound capable to inhibit cell wall synthesis like         benthiavalicarb, dimethomorph, flumorph, iprovalicarb,         mandipropamid, polyoxins, polyoxorim, validamycin A;     -   B11) a compound capable to inhibit melanine biosynthesis like         carpropamid, diclocymet, fenoxanil, phthalide, pyroquilon,         tricyclazole;     -   B12) a compound capable to induce a host defence like         acibenzolar-S-methyl, probenazole, tiadinil;     -   B13) a compound capable to have a multisite action like Bordeaux         mixture, captafol, captan, chlorothalonil, copper naphthenate,         copper oxide, copper oxychloride, copper preparations such as         copper hydroxide, copper sulphate, dichlofluanid, dithianon,         dodine, dodine free base, ferbam, fluorofolpet, folpet,         guazatine, guazatine acetate, iminoctadine, iminoctadine         albesilate, iminoctadine triacetate, mancopper, mancozeb, maneb,         metiram, metiram zinc, oxine-copper, propineb, sulphur and         sulphur preparations including calcium polysulphide, thiram,         tolylfluanid, zineb, ziram;     -   B14) a compound selected in the following list:         (2E)-2-(2-{[6-(3-chloro-2-methylphenoxy-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylacetamide,         (2E)-2-{2-[({[(1E)-1-(3-{[(E)-1-fluoro-2-phenylvinyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N-methylacetamide,         1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)cycloheptanol,         1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl-1H-imidazole-1-carboxylate,         1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1H-pyrazole-4-carboxamide,         2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine,         2-butoxy-6-iodo-3-propyl-4H-chromen-4-one,         2-chloro-N-(1,1,3-trimethyl-2,3-dihydro-1H-inden-4-yl)nicotinamide,         2-phenylphenol and salts,         3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,         3-(difluoromethyl)-N-[(9R)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-1H-pyrazole-4-carboxamide,         3-(difluoromethyl)N-[(9S)-9-isopropyl-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-1-methyl-1H-pyrazole-4-carboxamide,         3-(difluoromethyl)-N-[4′-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1H-pyrazole-4-carboxamide,         3,4,5-trichloropyridine-2,6-dicarbonitrile,         3-[5-(4-chlorophenyl)-2,3-dimethylisoxazolidin-3-yl]pyridine,         3-chloro-5-(4-chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine,         4-(4-chlorophenyl-5-(2,6-difluorophenyl)-3,6-dimethylpyridazine,         5-chloro-7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1,2,4]triazolo[1,5-a]pyrimidine,         8-hydroxyquinoline sulfate, benthiazole, bethoxazin, capsimycin,         carvone, chinomethionat, cufraneb, cyflufenamid, cymoxanil,         dazomet, debacarb, dichlorophen, diclomezine, dicloran,         difenzoquat, difenzoquat methylsulphate, diphenylamine, ecomate,         ferimzone, flumetover, fluopicolide, fluoroimide, flusulfamide,         fosetyl-aluminium, fosetyl-calcium, fosetyl-sodium,         hexachlorobenzene, irumamycin, isotianil, methasulfocarb, methyl         (2E)₂-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}thio)methyl]phenyl}-3-methoxyacrylate,         methyl         1-(2,2-dimethyl-2,3-dihydro-1H-inden-1-yl-1H-imidazole-5-carboxylate,         methyl isothiocyanate, metrafenone, mildiomycin,         N-(3′,4′-dichloro-5-fluorobiphenyl-2-yl)-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,         N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3-(formylamino)-2-hydroxybenzamide,         N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide,         N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,         N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2-yn-1-yloxy)phenyl]propanamide,         N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4-dichloronicotinamide,         N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4-dichloronicotinamide,         N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4-iodonicotinamide,         N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide,         N-{(Z)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide,         N-{2-[1,1′-bi(cyclopropyl)-2-yl]phenyl}-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,         N-{2-[3-chloro-5-(trifluoromethyl)pyridin-2-yl]ethyl}-2-(trifluoromethyl)benzamide,         natamycin,         N-ethyl-N-methyl-N′-{2-methyl-5-(trifluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide,         N-ethyl-N-methyl-N′-{2-methyl-5-(difluoromethyl)-4-[3-(trimethylsilyl)propoxy]phenyl}imidoformamide,         nickel dimethyldithiocarbamate, nitrothal-isopropyl,         O-{1-[(4-methoxyphenoxy)methyl]-2,2-dimethylpropyl}1H-imidazole-1-carbothioate,         octhilinone, oxamocarb, oxyfenthiin, pentachlorophenol and         salts, phosphorous acid and its salts, piperalin, propamocarb         fosetylate, propanosine-sodium, proquinazid, pyribencarb,         pyrrolnitrine, quintozene,         S-allyl-5-amino-2-isopropyl-4-(2-methylphenyl)-3-oxo-2,3-dihydro-1H-pyrazole-1-carbothioate,         tecloftalam, tecnazene, triazoxide, trichlamide, valiphenal,         zarilamid.

The composition according to the invention comprising a mixture of a compound of formula (I) or (Ia) to (Id) with a bactericide compound may also be particularly advantageous. Examples of suitable bactericide mixing partners may be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.

The compounds of formula (I) or (Ia) to (Id) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.

Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or (Ia) to (Id) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.

The method of treatment according to the invention may also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.

Among the plants that can be protected by the method according to the invention, mention may be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruit); Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); major crops such as Graminae sp. (for instance maize, lawn or cereals such as wheat, rice, barley and triticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (for instance colza), Fabacae sp. (for instance peanuts), Papilionaceae sp. (for instance soybean), Solanaceae sp. (for instance potatoes), Chenopodiaceae sp. (for instance beetroots) horticultural and forest crops; as well as genetically modified homologues of these crops.

Among the diseases of plants or crops that can be controlled by the method according to the invention, mention may be made of:

-   -   Powdery mildew diseases such as:     -   Blumeria diseases, caused for example by Blumeria graminis;     -   Podosphaera diseases, caused for example by Podosphaera         leucotricha;     -   Sphaerotheca diseases, caused for example by Sphaerotheca         fuliginea;     -   Uncinula diseases, caused for example by Uncinula necator;     -   Rust diseases such as:     -   Gymnosporangium diseases, caused for example by Gymnosporangium         sabinae;     -   Hemileia diseases, caused for example by Hemileia vastatrix;     -   Phakopsora diseases, caused for example by Phakopsora pachyrhizi         or Phakopsora meibomiae;     -   Puccinia diseases, caused for example by Puccinia recondita;     -   Uromyces diseases, caused for example by Uromyces         appendiculatus;     -   Oomycete diseases such as:     -   Bremia diseases, caused for example by Bremia lactucae;     -   Peronospora diseases, caused for example by Peronospora pisi         or P. brassicae     -   Phytophthora diseases, caused for example by Phytophthora         infestans;     -   Plasmopara diseases, caused for example by Plasmopara viticola;     -   Pseudoperonospora diseases, caused for example by         Pseudoperonospora humuli or Pseudoperonospora cubensis;     -   Pythium diseases, caused for example by Pythium ultimum;     -   Leafspot, leaf blotch and leaf blight diseases such as:     -   Alternaria diseases, caused for example by Alternaria solani;     -   Cercospora diseases, caused for example by Cercospora beticola;     -   Cladiosporum diseases, caused for example by Cladiosporium         cucumerinum;     -   Cochliobolus diseases, caused for example by Cochliobolus         sativus;     -   Colletotrichum diseases, caused for example by Colletotrichum         lindemuthanium;     -   Cycloconium diseases, caused for example by Cycloconium         oleaginum;     -   Diaporthe diseases, caused for example by Diaporthe citri;     -   Elsinoe diseases, caused for example by Elsinoe fawcettii;     -   Gloeosporium diseases, caused for example by Gloeosporium         laeticolor;     -   Glomerella diseases, caused for example by Glomerella cingulata;     -   Guignardia diseases, caused for example by Guignardia bidwelli;     -   Leptosphaeria diseases, caused for example by Leptosphaeria         maculans; Leptosphaeria nodorum;     -   Magnaporthe diseases, caused for example by Magnaporthe grisea;     -   Mycosphaerella diseases, caused for example by Mycosphaerella         graminicola Mycosphaerella arachidicola; Mycosphaerella         fijiensis;     -   Phaeosphaeria diseases, caused for example by Phaeosphaeria         nodorum;     -   Pyrenophora diseases, caused for example by Pyrenophora teres;     -   Ramularia diseases, caused for example by Ramularia collo-cygni;     -   Rhynchosporium diseases, caused for example by Rhynchosporium         secalis;     -   Septoria diseases, caused for example by Septoria apii or         Septoria lycopercisi;     -   Typhula diseases, caused for example by Typhula incamata;     -   Venturia diseases, caused for example by Venturia inaequalis;     -   Root and stem diseases such as:     -   Corticium diseases, caused for example by Corticium graminearum;     -   Fusarium diseases, caused for example by Fusarium oxysporum;     -   Gaeumannomyces diseases, caused for example by Gaeumannomyces         graminis;     -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;     -   Tapesia diseases, caused for example by Tapesia acuformis;     -   Thielaviopsis diseases, caused for example by Thielaviopsis         basicola;     -   Ear and panicle diseases such as:     -   Alternaria diseases, caused for example by Alternaria spp.     -   Aspergillus diseases, caused for example by Aspergillus flavus;     -   Cladosporium diseases, caused for example by Cladosporium spp.     -   Claviceps diseases, caused for example by Claviceps purpurea;     -   Fusarium diseases, caused for example by Fusarium culmorum;     -   Gibberella diseases, caused for example by Gibberella zeae;     -   Monographella diseases, caused for example by Monographella         nivalis;     -   Smut and bunt diseases such as:     -   Sphacelotheca diseases, caused for example by Sphacelotheca         reiliana;     -   Tilletia diseases, caused for example by Tilletia caries;     -   Urocystis diseases, caused for example by Urocystis occulta;     -   Ustilago diseases, caused for example by Ustilago nuda;     -   Fruit rot and mould diseases such as:     -   Aspergillus diseases, caused for example by Aspergillus flavus;     -   Botrytis diseases, caused for example by Botrytis cinerea;     -   Penicillium diseases, caused for example by Penicillium         expansum;     -   Sclerotinia diseases, caused for example by Sclerotinia         sclerotiorum;     -   Verticilium diseases, caused for example by Verticilium         alboatrum;     -   Seed and soilborne decay, mould, wilt, rot and damping-off         diseases such as:     -   Fusarium diseases, caused for example by Fusarium culmorum;     -   Phytophthora diseases, caused for example by Phytophthora         cactorum;     -   Pythium diseases, caused for example by Pythium ultimum;     -   Rhizoctonia diseases, caused for example by Rhizoctonia solani;     -   Sclerotium diseases, caused for example by Sclerotium rolfsii;     -   Microdochium diseases, caused for example by Microdochium         nivale;     -   Canker, broom and dieback diseases such as:     -   Nectria diseases, caused for example by Nectria galligena;     -   Blight diseases such as:     -   Monilinia diseases, caused for example by Monilinia laxa;     -   Leaf blister or leaf curl diseases such as:     -   Taphrina diseases, caused for example by Taphrina deformans;     -   Decline diseases of wooden plants such as:     -   Esca diseases, caused for example by Phaemoniella clamydospora;     -   Eutypa dyeback, caused for example by Eutypa lata;     -   Dutch elm disease, caused for example by Ceratocystsc ulmi;     -   Diseases of flowers and Seeds such as:     -   Botrytis diseases, caused for example by Botrytis cinerea;     -   Diseases of tubers such as:     -   Rhizoctonia diseases, caused for example by Rhizoctonia solani.

The fungicide composition according to the invention may also be used against fungal diseases liable to grow on or inside timber. The term “timber” means all types of species of wood, and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood, and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention, or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.

The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 150 g per 100 kg of seed in the case of seed treatment.

It is clearly understood that the doses indicated herein are given as illustrative examples of the method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated.

The fungicide composition according to the invention may also be used in the treatment of genetically modified organisms with the compounds according to the invention or the agrochemical compositions according to the invention. Genetically modified plants are plants into genome of which a heterologous gene encoding a protein of interest has been stably integrated. The expression “heterologous gene encoding a protein of interest” essentially means genes which give the transformed plant new agronomic properties, or genes for improving the agronomic quality of the modified plant.

The compounds or mixtures according to the invention may also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.

The following tables I-III illustrate in a non-limiting manner examples of compounds according to the invention.

In the following compound examples, M+H indicates the mass versus charge (m/z value) of the monoprotonated molecular ion, as observed in mass spectroscopy by positive atmospheric-pressure chemical-ionisation (APCI+) or positive electrospray-ionisation (ES+).

In the following examples, the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below:

Temperature: 40° C.; Mobile phases: 0.1% aqueous formic acid and acetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile. Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). The lambda max values were determined in the maxima of the chromatographic signals using the UV spectra from 190 nm to 400 nm.

TABLE I (Ic)

N^(o) A L¹ —L²—Q E² LogP M + H 1

—CH₂—

Me 3.26 454 2

—CH₂—

Me 3.27 434 3

—CH₂—

Me 3.65 448 4

—CH₂—

Me 3.26 460 5

—CH₂—

Me 3 460 6

—CH₂—

Me 2.73 424 7

—CH₂—

Me 3.3 452 8

—CH₂—

Me 4.48 466 9

—CH₂—

Me 3.45 488 10

—CH₂—

Me 3.21 474 11

—CH₂—

Me 4.77 496 12

—CH₂—

Me 2.86 426 13

—CH₂—

Me 3.59 454 14

—CH₂—

Me 1.39 350 15

—CH₂—

Me 2.61 466 16

—CH₂—

Me 4.19 464 17

—CH₂—

Me 2.66 452 18

—CH₂—

Me 2.94 19

—CH₂—

Me 1.28 316 20

—CH₂—

Me 1.32 325 21

—CH₂—

Me 2.88 441 22

—CH₂—

Me 2.99 435 23

—CH₂—

Me 3.26 477 24

—CH₂—

Me 2.86 469 25

—CH₂—

Me 2.92 447 26

—CH₂—

Me 2.32 407 27

—CH₂—

Me 2.22 405 28

—CH₂—

Me 2.65 433 29

—CH₂—

Me 3.32 432 30

—CH₂—

Me 3.25 420 31

—CH₂—

Me 2.55 392 32

—CH₂—

Me 2.9 440 33

—CH₂—

Me 3.14 454 34

—CH₂—

Me 2.67 426 35

—CH₂—

Me 2.93 426 36

—CH₂—

Me 3.39 37

—CH₂—

Me 3 400 38

—CH₂—

Me 3.01 420 39

—CH₂—

Me 3.05 418 40

—CH₂—

Me 2.51 390 41

—CH₂—

Me 4.51 462 42

—CH₂—

Et 3.35 420 43

—CH₂—

Et 3.04 406 44

—CH₂—

Me 3.46 470 45

—CH₂—

Me 3.49 468 46

—CH₂—

Me 3.24 456 47

—CH₂—

Me 3.65 485 48

—CH₂—

Me 2.28 438 49

—CH₂—

Me 2.3 424 50

—(CH₂)₂—

Me 1.16 336 51

—(CH₂)₂—

Me 3.19 420 52

—CH₂—

Me 398 53

—CH₂—

Me 4.24 482 54

—CH₂—

Me 4.08 516 55

—CH₂—

Me 3.7 466 56

—CH₂—

Me 3.87 468 57

—CH₂—

Me 4.58 496 58

—CH₂—

Me 1.47 320 59

—CH₂—

Me 2.95 404 60

—CH₂—

Me 3.4 466 61

—CH₂—

Me 3.15 452 62

—CH₂—

Me 2.98 416 63

—CH₂—

Me 2.96 424 64

—CH₂—

Me 3.26 418 65

—CH₂—

Me 2.92 438 66

—CH₂—

Me 2.57 390 67

—CH₂—

Me 3.12 468 68

—CH₂—

Me 2.41 388 69

—CH₂—

Me 2.42 388 70

—CH₂—

Me 2.23 436 71

—CH₂—

Me 2.37 422 72

—CH₂—

Me 1 314 73

—CH₂—

Me 2.53 416 74

—CH₂—

Me 4.04 428 75

—CH₂—

Me 3.78 462 76

—CH₂—

Me 2.86 432 77

—CH₂—

Me 4.03 500 78

—CH₂—

Me 5.94 572 79

—CH₂—

Me 4.18 502 80

—CH₂—

Me 4.88 530 81

—CH₂—

Me 2.83 450 82

—CH₂—

Me 4.11 520 83

—CH₂—

Me 5.85 590 84

—CH₂—

Me 3.83 518 85

—CH₂—

Me 4.78 548 86

—CH₂—

Me 2.07 402 87

—CH₂—

Me 3.74 486 88

—CH₂—

Me 4.04 547 89

—CH₂—

Me 3.76 533 90

—CH₂—

Me 3.66 497 91

—CH₂—

Me 3.61 505 92

—CH₂—

Me 3.92 499 93

—CH₂—

Me 3.53 519 94

—CH₂—

Me 3.22 471 95

—CH₂—

Me 3.76 549 96

—CH₂—

Me 3.04 469 97

—CH₂—

Me 3.08 469 98

—CH₂—

Me 2.94 518 99

—CH₂—

Me 3.1 502 100

—CH₂—

Me 2.02 356 101

—CH₂—

Me 3 424 102

—CH₂—

Me 3.73 440 103

—CH₂—

Me 3.62 104

—CH₂—

Me 3.64 503 105

—CH₂—

Me 3.32 489 106

—CH₂—

Me 4.12 454 107

—CH₂—

Me 4.12 108

—CH₂—

Me 3.85 488 109

—CH₂—

Me 3.93 490 110

—CH₂—

Me 4.24 504 111

—CH₂—

Me 2.88 472 112

—CH₂—

Me 3.05 458 113

—CH₂—

Me 1.8 336 114

—CH₂—

Me 2.88 406 115

—CH₂—

Me 3.42 420 116

—CH₂—

Me 3.35 454 117

—CH₂—

Me 3.17 469 118

—CH₂—

Me 3.33 483 119

—CH₂—

Me 2.84 404 120

—CH₂—

Me 3.76 434 121

—CH₂—

Me 3.81 482 122

—CH₂—

Me 3.54 468 123

—CH₂—

Me 3.88 484 124

—CH₂—

Me 1.51 330 125

—CH₂—

Me 4.02 478 126

—CH₂—

Me 4.34 444 127

—CH₂—

Me 3.79 428 128

—CH₂—

Me 3.06 477 129

—CH₂—

Me 2.6 452 130

—CH₂—

Me 2.76 438 131

—CH₂—

Me 2.13 382 132

—CH₂—

Me 3.28 542 133

—CH₂—

Me 3.8 480 134

—CH₂—

Me 3.27 452 135

—CH₂—

Me 5.01 522 136

—CH₂—

Me 3.39 486 137

—CH₂—

Me 3.17 450 138

—CH₂—

Me 3.14 450 139

—CH₂—

Me 3.58 500 140

—CH₂—

Me 4.05 528 141

—CH₂—

Me 3.32 498 142

—CH₂—

Me 2.03 466 143

—CH₂—

Me 4.29 496

TABLE II (Id)

N^(o) A L¹ —L²—Q E² LogP M + H 144

—CH₂—

Me 2.6 398 145

—CH₂—

Me 3.88 466 146

—CH₂—

Me 4.87 496 147

—CH₂—

Me 4.18 468 148

—CH₂—

Me 4.52 482 149

—CH₂—

Me 2.02 356 150

—CH₂—

Me 4.29 516

TABLE III (Ia)

N^(o) A L¹ —L²—Q E¹ LogP M + H 151

—CH₂—

Me 1.17 322 152

—CH₂—

Me 3.17 406 153

—CH₂—

Me 3.39 456 154

—CH₂—

Me 2.39 438 155

—(CH₂)₂—

Me 304 156

—(CH₂)₂—

Me 321 157

—CH₂—

Me 317 158

—CH₂—

Me 1.42 356 159

—CH₂—

Me 3.72 470 160

—CH₂—

Me 3.37 454 161

—CH₂—

Me 3.62 490 162

—CH₂—

Me 3.25 460 163

—CH₂—

Me 3.19 474 164

—CH₂—

Me 1.81 399 165

—CH₂—

Me 3.85 533 166

—CH₂—

Me 4.06 547 167

—CH₂—

Me 4.29 513 168

—CH₂—

Me 3.85 467 169

—CH₂—

Me 3.62 503 170

—CH₂—

Me 3.62 483 171

—CH₂—

Me 3.94 497 172

—CH₂—

Me 3.58 517 173

—CH₂—

Me 3.46 523 174

—CH₂—

Me 1.57 393 175

—CH₂—

Me 3.72 511 176

—CH₂—

Me 3.7 477 177

—CH₂—

Me 4.56 507 178

—CH₂—

Me 4.06 491 179

—CH₂—

Me 497

The following examples illustrate in a non-limiting manner the preparation of the compounds of formula (I) according to the invention.

5-Methyl-1-(3-thiophenecarbohydroximoyl)-tetrazole and 5-methyl-2-(3-thiophenecarbohydroximoyl)-tetrazole

To a solution of 3-thiophene carboxaldehyde oxime (8 g, 62.9 mmol) in DMF (80 ml) is added N-chlorosuccinimide (8.8 g, 66 mmol) portionwise, while maintaining the reaction temperature below 45° C. On complete addition, the mixture is stirred one hour at room temperature before being poured into a saturated aqueous NH₄Cl solution. The mixture is extracted with ethyl acetate. The organic layer is washed successively with water and brine, dried (MgSO₄), filtered and concentrated. The residue and 5-methyltetrazole (5.3 g, 62.9 mmol) are diluted in dichloromethane (80 ml) and triethyamine (11.4 ml, 82.1 mmol) is added dropwise at room temperature. After stirring overnight, a saturated aqueous NH₄Cl solution is added. The aqueous layer is extracted with ethyl acetate. The combined organic layers are washed successively with water and brine, dried (MgSO₄), filtered and concentrated. Silica-gel chromatography of the residue affords 5.5 g of 5-methyl-1-(3-thiophenecarbohydroximoyl)-tetrazole [yield 37.6%; ¹H-NMR (DMSO-d6) δ_(ppm): 2.48 (s, 3H), 7.42 (d, 1H), 7.51 (d, 1H), 7.74 (dd, 1H), 12.7 (s, 1H)] and 2 g 5-methyl-2-(3-thiophenecarbohydroximoyl)-tetrazole [yield 13.7% ¹H-NMR (DMSO-d6) δ_(ppm): 2.62 (s, 3H), 7.40 (m, 2H), 7.73 (dd, 1H), 12.6 (s, 1H)].

O-(2-Amino-1,3-thiazol-4-yl)methyl-(thien-3-yl)-(5-methyltetrazol-1-yl)methanone oxime (compound 20)

To a cooled solution (0-5° C.) of 5-methyl-1-(3-thiophenecarbohydroximoyl)tetrazole (18.7 g, 89.4 mmol) in acetonitrile (100 ml) is added DBN (22.4 ml, 187.7 mmol). On complete addition, the mixture is stirred five minutes and 4-chloromethyl-2-amino-1,3-thiazole hydrochloride (18.2 g, 98.3 mmol) is added portionwise. On complete addition, the mixture is stirred five minutes before the removal of the cooling bath. After stirring overnight, the solvent is evaporated. Silica-gel chromatography of the residue affords 18.4 g of compound 20 [yield 60.8%; HPLC/MS: m/z=325 (M+H); LogP=1.32].

O-(2-tert-Butylcarbonylamino-1,3-thiazol-4-yl)methyl-(thien-3-yl)-(5-methyltetrazol-1-yl)methanone oxime (compound 18)

To a cooled solution (0-5° C.) of compound 20 (8 g, 24.9 mmol) in dry dichloromethane (250 ml) are added triethylamine (3.6 ml, 26.1 mmol) and a catalytic quantity of DMAP, then pivaloyl chloride (3.2 ml, 26.1 mmol) is added dropwise. On complete addition, the mixture is stirred ten minutes before the removal of the cooling bath. After stirring overnight, water is added. After separation, the organic layer is dried (MgSO₄), filtered and concentrated to give an off-white solid. Trituration with methanol, filtration, washing with methanol and drying affords 3.2 g of compound 18 [yield 60.5%; HPLC/MS: m/z=406 (M+H); LogP=2.94].

(2-Phenyl-1,3-thiazol-4-yl)-(1-methyltetrazol-5-yl)methanone

To a solution of 1-methyltetrazole (2 g, 23.8 mmol) and TMEDA (10 ml, 66.2 mmol) in THF (100 ml) cooled at −78° C. is added dropwise 2.5 M nBuLi in hexanes (9.5 ml, 23.8 mmol) with vigorous stirring and maintaining the reaction temperature below −65° C. On complete addition, the mixture is stirred 20 minutes before adding dropwise a solution of N-methyl-N-methoxy-2-phenyl-1,3-thiazol-4-yl)carboxamide (5.9 g, 23.8 mmol) in THF. On complete addition, the mixture is stirred for six hours at −78° C. before adding slowly a solution of 1N HCl in water (100 ml). When the reaction mixture reaches room temperature, water is added (500 ml) and the reaction mixture is neutralised with a saturated aqueous NaHCO₃ solution and extracted with ethyl acetate (500 ml). After separation, the organic layer is dried (MgSO₄), filtered and concentrated. Silica-gel chromatography of the residue affords 4.7 g of (2-phenyl-1,3-thiazol-4-yl)-1-methyltetrazol-5-yl)methanone [yield 72.8%; ¹H-NMR (CDCl₃) δ_(ppm): 4.48 (s, 3H), 7.5 (m, 3H), 8.08 (m, 2H), 9.44 (s, 1H)].

1-Methyl-5-[(2-phenyl-1,3-thiazol-4-yl)carbohydroximoyl]tetrazole

A solution of 1-methyl-5-[(2-phenyl-1,3-thiazol-4-yl)carbohydroximoyl]tetrazole (5.1 g, 18.8 mmol) and hydroxylamine hydrochloride (3.3 g, 47 mmol) in pyridine (60 ml) is stirred three hours at 50° C. and overnight at room temperature. The solvent is evaporated and water is added to the crude mixture. The resulting suspension is filtered. The solid is washed with water and dried to give 5 g of 1-methyl-5-[(2-phenyl-1,3-thiazol-4-yl)carbohydroximoyl]tetrazole [yield 92.9%; ¹H-NMR (DMSO-d6) δ_(ppm): 4.08 (s, 3H), 7.5 (m, 3H), 7.9 (m, 2H), 8.02 (s, 1H), 12.9 (s, 1H)].

O-(2-Phtalimidopyridin-6-yl)methyl-(2-phenyl-1,3-thiazol-4-yl)-(1-methyitetrazol-5-yl)methanone oxime (compound 173)

To a cooled solution (0-5° C.) of 1-methyl-5-[(2-phenyl-1,3-thiazol-4-yl)carbohydroximoyl]tetrazole (2.5 g, 8.7 mmol) in acetonitrile (10 ml) is added DBN (2.2 ml, 18.3 mmol). On complete addition, the mixture is stirred five minutes and 6-bromomethyl-2-phtalimidopyridine (3.05 g, 9.6 mmol) is added portionwise. On complete addition, the mixture is stirred five minutes before the removal of the cooling bath. After stirring overnight, water is added and the reaction mixture is extracted with ethyl acetate. The organic layer is dried (MgSO₄), filtered and concentrated. Silica-gel chromatography of the residue affords 2.1 g of compound 173 [yield 41.4%; HPLC/MS: m/z=523 (M+H); LogP=3.46].

O-(2-Aminopyridin-6-yl)methyl-(2-phenyl-1,3-thiazol-4-yl)-(1-methyltetrazol-5-yl)methanone oxime (compound 174)

To a solution of compound 173 (1.8 g, 3.1 mmol) in THF (45 ml) is added hydrazine hydrate (0.75 ml, 15.5 mmol). After stirring overnight, the reaction mixture is filtered and concentrated. Silica-gel chromatography of the residue affords 1 g of compound 174 [yield 82.2%; HPLC/MS m/z=393 (M+H); LogP=1.57].

O-(2-Pentylcarbonylaminopyridin-6-yl)methyl-(2-phenyl-1,3-thiazol-4-yl)-(1-methyitetrazol-5-yl)methanone oxime (compound 178)

To a solution of compound 174 (0.15 g, 0.38 mmol) in dry dichloromethane (5 ml) are added resin PS-BEMP 2.2 mmol/g (0.34 g) and hexanoyl chloride (77 mg, 0.57 mmol). After stirring overnight, the reaction mixture is filtered and concentrated. Silica-gel chromatography of the residue affords 0.16 g of compound 178 [yield 61.8%; HPLC/MS: m/z=491 (M+H); LogP=4.06].

The following examples illustrate in a non-limiting manner the biological activity of the compounds of formula (I) according to the invention.

EXAMPLE A In Vivo Test on Peronospora parasitica (Crucifer Downy Mildew)

Cabbage plants (Eminence variety) in starter cups, sown on a 50/50 peat soil-pozzolana substrate and grown at 18-20° C., are treated at the cotyledon stage by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Peronospora parasitica spores (50 000 spores per ml). The spores are collected from infected plant. The contaminated cabbage plants are incubated for 5 days at 20° C., under a humid atmosphere. Grading is carried out 5 days after the contamination, in comparison with the control plants.

Under these conditions, good protection (at least 70%) is observed at a dose of 500 ppm with the following compounds: 1, 2, 3, 5, 13, 16, 17, 18, 19, 20, 22, 23, 24, 25, 26, 27, 28, 30, 31, 32, 33, 34, 36, 37, 38, 39, 42, 43, 44, 46, 48, 49, 50, 51, 62, 63, 64, 65, 66, 67, 68, 69, 72, 73, 74, 75, 88, 90, 92, 93, 95, 96, 97, 98, 101, 106, 107, 110, 111, 112, 114, 115, 116, 118, 119, 120, 123, 124, 125, 126, 127, 128, 129, 130, 151, 152, 153 and 154.

EXAMPLE B In Vivo Test on Phytophthora infestans (Tomato Late Blight)

Tomato plants (Marmande variety) sown in started cups on a 50/50 peat soil-pozzolana subtrate and grown at 20-25° C., are treated at stage Z¹⁶ by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying them with an aqueous suspension of Phytophthora infestans spores (20 000 spores per ml). The spores are collected from infected plants. The contaminated tomato plants are incubated for 5 days at 20° C., under a humid atmosphere. Grading is carried out 5 days after the contamination, in comparison with the control plants.

Under these conditions, good protection (at least 70%) is observed at a dose of 500 ppm with the following compounds: 3, 18, 19, 22, 24, 36, 38, 95, 101, 124, 126, 127 and 152.

EXAMPLE C In Vivo Test on Plasmopara parasitica (Vine Downy Mildew)

Vine plants (Cabernet variety) grown on a 50/50 peat soil-pozzolana subtrate at 20-22° C., are treated at stage Z¹⁵ by spraying with the aqueous suspension described above. Plants, used as controls, are treated with an aqueous solution not containing the active material. After 24 hours, the plants are contaminated by spraying the lower surface of the leaves with an aqueous suspension of Plasmopara viticola spores (100 000 spores per ml). The spores are collected from infected plants. The contaminated vine plants are incubated for 7 to 8 days at 20° C., under humid atmosphere. Grading is carried out 7 to 8 days after the contamination, in comparison with the control plants.

Under these conditions, good protection (at least 70%) is observed at a dose of 500 ppm with the following compounds: 16, 18, 19, 22, 24, 28, 42, 43, 67, 88, 90, 92, 95, 96, 97, 101, 106, 110, 116, 119, 124, 125, 126, 127, 128 and 152.

EXAMPLE D Cell Test on Pythium ultimum (Damping-Off)

The growth of Pythium ultimum is performed in PDB medium at 20° C. during 7 days. The PDB medium is prepared by mixing 24 grams of PDB (Difco) in 1 liter of demineralized water. The medium is sterilized by autoclave 15 minutes at 121° C. After 7 days of growth, the mycelium of Pythium ultimum is ground and is used as inoculum. The compounds are solubilized in DMSO and added to sterile liquid glucose/mycopeptone medium (14.6 g/l of D-glucose, 7.1 g/l of mycological peptone (Oxoid) and 1.4 g/l of yeast extract (Merck)) at a concentration of 2 ppm. The medium is inoculated with the ground mycelium at an initial OD at 620 nm of 0.025. The efficacy of the compounds is assessed by OD measurement at 620 nm after 5 days at 20° C. in comparison with a control.

Under these conditions, good protection (at least 70%) is observed at a dose of 6 ppm with the following compounds: 1, 2, 3, 4, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 19, 21, 22, 23, 24, 25, 26, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 44, 45, 46, 47, 48, 59, 60, 63, 64, 65, 67, 68, 74, 75, 86, 87, 88, 90, 91, 92, 93, 94, 95, 96, 97, 98, 100, 101, 102, 103, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 129, 134, 138, 151, 152, 153, 154, 160, 166, 170, 175, 177 and 178. 

1. A compound of formula (I)

wherein T represents a substituted or non-substituted tetrazolyl group; L¹ represents a direct bond or a divalent group selected in the list consisting of —(CR¹R²)_(n)— —(CR¹R²)_(m)—C(═O)—(CR¹R²)_(p)— —(CR¹R²)_(m)—(CR¹═CR²)—(CR¹R²)_(p)— —(CR¹R²)_(m)—C(═O)—O—(CR¹R²)_(p) —(CR¹R²)_(m)—C≡C—(CR¹R²)_(p)— —(CR¹R²)_(m)—O—C(═O)—(CR¹R²)_(p)— —(CR¹R²)_(m)—O—(CR¹R²)_(p)— —(CR¹R²)_(m)—C(═O)—NH—(CR¹R²)_(p)— —(CR¹R²)_(m)—NH—(CR¹R²)_(p)— —(CR¹R²)_(m)—NH—C(═O)—(CR¹R²)_(p)— wherein n represents 1, 2, 3 or 4; m and p independently represent 0, 1, 2 or 3; L² represents a direct bond or a divalent group selected in the list consisting of —(CR³R⁴)_(q)— —(CR³R⁴)_(a)—C(═O)—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—(CR³═CR⁴)—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—C(═O)—O—(CR³R⁴)_(b) —(CR³R⁴)_(a)—C≡C—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—O—C(═O)—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—O—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—C(═O)—NH—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—NH—(CR³R⁴)_(b)— —(CR³R⁴)_(a)—NH—C(═O)—(CR³R⁴)_(b)— wherein q represents 1, 2, 3 or 4; a and b independently represent 0, 1, 2 or 3; A is selected in the list consisting of A¹ to A¹¹⁶

wherein Z¹, Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁵, —C(═O)OR⁵, —C(═O)NR⁵R⁶, —C(═O)SR⁵, —C(═S)R⁵, —C(═S)OR⁵, —C(═S)NR⁵R⁶, —C(═S)SR⁵, —CR⁵═NR⁶, —CR⁵═NOR⁶, —CR⁵═N—NR⁶R⁷, —OR⁵, —OSiR⁵R⁶R⁷, —OC(═O)R⁵, —OC(═O)OR⁵, —OC(═O)NR⁵R⁶, —OC(═S)NR⁵R⁶, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, —N(R⁵)C(═O)NR⁶R⁷, —N(R⁵)C(═S)R⁶, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶, —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)OR⁶, —N(R⁵)NR⁶R⁷, —N═NR⁵, —N(R⁵)S(═O)R⁶, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)OR⁶, —N(R⁵)S(═O)NR⁶R⁷, —N(R⁵)S(═O)₂NR⁶R⁷, —SR⁵, —S(═O)R⁵, —S(═O)₂R⁵, —S(═O)OR⁵, —S(═O)NR⁵R⁶, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶, nitro, nitroso, azido, cyano, —SF₅ and —SiR⁵R⁶R⁷; K¹ and K² are independently selected in the list consisting of hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁹, —C(═O)OR⁹, —C(═O)NR⁹R¹⁰, —C(═O)SR⁹, —C(═S)R⁹, —C(═S)OR⁹, —C(═S)NR⁹R¹⁰, —C(═S)SR⁹, —CR⁹═NR¹⁰, —CR⁹═NOR¹⁰, —CR⁹═N—NR¹⁰R¹¹, —S(═O)R⁹, —S(═O)₂R⁹, —S(═O)OR⁹, —S(═O)NR⁹R¹⁰, —S(═O)₂OR⁹, —S(═O)₂NR⁹R¹⁰ and —SiR⁹R¹⁰R¹¹; G¹ and G² are independently selected in the list consisting of oxygen, sulfur, NR¹², N—OR¹² and N—NR¹²R¹³; Q is selected in the list consisting of Q¹ to Q⁷²

wherein X¹, X², X³, X⁴ and X⁵ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁴, —C(═O)OR¹⁴, —C(═O)NR¹⁴R¹⁵, —C(═O)SR¹⁴, —C(═S)R¹⁴, —C(═S)OR¹⁴, —C(═S)NR¹⁴R¹⁵, —C(═S)SR¹⁴, —CR¹⁴═NR¹⁵, —CR¹⁴═NOR¹⁵, —CR¹⁴═N—NR¹⁵R¹⁶, —OR¹⁴, —OSiR¹⁴R¹⁵R¹⁶, —OC(═O)R¹⁴, —OC(═O)OR¹⁴, —OC(═O)NR¹⁴R¹⁵, —OC(═S)NR¹⁴R¹⁵, —NR¹⁴R¹⁵, —N(R¹⁴)C(═O)R¹⁵, —N(R¹⁴)C(═O)OR¹⁵, —N(R¹⁴)C(═O)NR¹⁵R¹⁶, —N(R¹⁴)C(═S)R¹⁵, —N(R¹⁴)C(═S)NR¹⁵R¹⁶, —N═CR¹⁴R¹⁵, —N═C—NR¹⁴R¹⁵, —N(R¹⁴)C(═NR¹⁵)NR¹⁶R¹⁷, —N(R¹⁴)OR¹⁵, —N(R¹⁴)NR¹⁵R¹⁶, —N═NR¹⁴, —N(R¹⁴)S(═O)R¹⁵, —N(R¹⁴)S(═O)₂R¹⁵, —N(R¹⁴)S(═O)₂OR¹⁵, —N(R¹⁴)S(═O)OR¹⁵, —N(R¹⁴)S(═O)NR¹⁵R¹⁶, —N(R¹⁴)S(═O)₂NR¹⁵R¹⁶, —SR¹⁴, —S(═O)R¹⁴, —S(═O)₂R¹⁴, —S(═O)OR¹⁴, —S(═O)NR¹⁴R¹⁵, —S(═O)₂OR¹⁴, —S(═O)₂NR¹⁴R¹⁵, nitro, nitroso, azido, cyano, —SF₅ and —SiR¹⁴R¹⁵R¹⁶; W¹ is selected in the list consisting of hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R⁹, —C(═O)OR⁹, —C(═O)NR⁹R¹⁰, —C(═O)SR⁹, —C(═S)R⁹, —C(═S)OR⁹, —C(═S)NR⁹R¹⁰, —C(═S)SR⁹, —CR⁹═NR¹⁰, —CR⁹═NOR¹⁰, —CR⁹═N—NR¹⁰R¹¹, —S(═O)R⁹, —S(═O)₂R⁹, —S(═O)OR⁹, —S(═O)NR⁹R¹⁰, —S(═O)₂OR⁹, —S(═O)₂NR⁹R¹⁰ and —SiR⁹R¹⁰R¹¹; R¹, R², R³ and R⁴ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, [C₁-C₄]-alkoxy, [C₁-C₄]-alkoxy-[C₁-C₄]-alkyl, [C₁-C₄]-alkoxy-[C₁-C₄]-alkoxy, [C₁-C₄]-haloalkoxy, [C₁-C₄]-haloalkoxy-[C₁-C₄]-alkyl and cyano; R⁵ to R¹⁷ are independently selected in the list consisting of hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl and aryl-[C₁-C₈]-alkyl; as well as salts, N-oxides, metallic complexes and metalloidic complexes thereof.
 2. A compound according to claim 1 and selected in the list of compounds of formula (Ia) to (Id)

wherein A, Q, L¹ and L² are defined in the same manner as the corresponding substituents of the compounds of formula (I) according to claim 1; E¹ is selected in the list consisting of hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —C(═O)SR¹⁸, —C(═S)R¹⁸, —C(═S)OR¹⁸, —C(═S)NR¹⁸R¹⁹, —C(═S)SR¹⁸, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)R¹⁸, —S(═O)₂R¹⁸, —S(═O)OR¹⁸, —S(═O)NR¹⁸R¹⁹, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano, and —SiR¹⁸R¹⁹R²⁰; E² is selected in the list consisting of hydrogen, halogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl, aryl-[C₁-C₈]-alkyl, hydroxy-[C₁-C₈]-alkyl, [C₁-C₈]-alkoxy-[C₁-C₈]-alkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —C(═O)SR¹⁸, —C(═S)R¹⁸, —C(═S)OR¹⁸, —C(═S)NR¹⁸R¹⁹, —C(═S)SR¹⁸, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸, —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)OR¹⁸, —OC(═O)NR¹⁸R¹⁹, —OC(═S)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹, —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰, —N═CR¹⁸R¹⁹, —N═C—NR¹⁸R¹⁹, —N(R¹⁸)C(═NR¹⁹)NR²⁰R²¹, —N(R¹⁸)OR¹⁹, —N(R¹⁸)NR¹⁹R²⁰, —N═NR¹⁸, —N(R¹⁸)S(═O)R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹, —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)OR¹⁹, —N(R¹⁸)S(═O)NR¹⁹R²⁰, —N(R¹⁸)S(═O)₂NR¹⁹R²⁰, —SR¹⁸, —S(═O)R¹⁸, —S(═O)₂R¹⁸, —S(═O)OR¹⁸, —S(═O)NR¹⁸R¹⁹, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano, —SF₅ and —SiR¹⁸R¹⁹R²⁰; R¹⁸ to R²¹ are independently selected in the list consisting of hydrogen, [C₁-C₈]-alkyl, [C₁-C₈]-haloalkyl, [C₂-C₈]-alkenyl, [C₂-C₈]-haloalkenyl, [C₂-C₈]-alkynyl, [C₂-C₈]-haloalkynyl, [C₃-C₆]-cycloalkyl, [C₃-C₆]-halocycloalkyl, aryl and aryl-[C₁-C₈]-alkyl.
 3. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein L¹ represents a direct bond or a divalent group selected in the list consisting of —(CR¹R²)_(n)— —C(═O)—(CR¹R²)_(p)— —(CR¹R²)_(m)—O— —(CR¹R²)_(m)—C(═O)—O— —(CR¹R²)_(m)—NH— —(CR¹R²)_(m)—C(═O)—NH— —(CR¹R²)_(m)—C(═O)— —(CR¹R²)_(m)—NH—C(═O) wherein n represents 1 or 2; m and p independently represent 0 or 1; R¹ and R² are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-alkynyl, [C₃-C₅]-cycloalkyl, [C₁-C₄]-alkoxy, [C₁-C₄]-haloalkoxy and cyano.
 4. A compound of formula (I) and (Ia) to (Id) according to claim 3 wherein L¹ represents a direct bond or a divalent group selected in the list consisting of —(CR¹R²)—, —C(═O)—(CR¹R²)— and —C(═O)—; wherein R¹ and R² are independently selected in the list consisting of hydrogen, halogen, methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy and cyano.
 5. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein L² represents a direct bond or a divalent group selected in the list consisting of —(CR³R⁴)_(q)— —(CR³R⁴)_(a)—C(═O)— —(CR³═CR⁴)— —(CR³R⁴)_(a)—C(═O)—O— —C≡C— —(CR³R⁴)_(a)—O—C(═O)— —(CR³R⁴)_(a)—O— —(CR³R⁴)_(a)—C(═O)—NH— —(CR³R⁴)_(a)—NH— —(CR³R⁴)_(a)—NH—C(═O)— wherein q and a independently represent 1 or 2; R³ and R⁴ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-alkynyl, [C₃-C₅]-cycloalkyl, [C₁-C₄]-alkoxy, [C₁-C₄]-haloalkoxy and cyano.
 6. A compound of formula (I) and (Ia) to (Id) according to claim 5 wherein L² represents a direct bond or —(CR³R⁴)— wherein R³ and R⁴ are independently selected in the list consisting of hydrogen, halogen, methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy and cyano.
 7. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein A is selected in the list consisting of A¹ to A³².
 8. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein A is selected in the list consisting of A², A⁶, A⁸, A¹⁵, A¹⁶, A¹⁷ and A¹⁸.
 9. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein Z¹ is selected in the list consisting of hydrogen, —C(═O)R⁵, —C(═O)OR⁵, —C(═O)NR⁵R⁶, —C(═S)NR⁵R⁶, —CR⁵NR⁶, —CR⁵═NOR⁶, —CR⁵═N—NR⁶R⁷, —OR⁵, —OC(═O)R⁵, —OC(═O)OR⁵, —OC(═O)NR⁵R⁶, —OC(═S)NR⁵R⁶, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, —N(R⁵)C(═O)NR⁶R⁷, —N(R⁵)C(═S)R⁶, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶, —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)OR⁶, —N(R⁵)NR⁶R⁷, —N═NR⁵, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)₂NR⁶R⁷, —SR⁵, —S(═O)₂R⁵, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶ and cyano.
 10. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein Z¹ is selected in the list consisting of hydrogen, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —N(R⁵)C(═O)OR⁶, —N(R⁵)C(═O)NR⁶R⁷, —N(R⁵)C(═S)NR⁶R⁷, —N═CR⁵R⁶, —N═C—NR⁵R⁶, —N(R⁵)C(═NR⁶)NR⁷R⁸, —N(R⁵)S(═O)₂R⁶, —N(R⁵)S(═O)₂OR⁶, —N(R⁵)S(═O)₂NR⁶R⁷ and cyano.
 11. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, —C(═O)R⁵, —C(═O)OR⁵, —C(═O)NR⁵R⁶, —OR⁵, —OSiR⁵R⁶R⁷, —OC(═O)R⁵, —NR⁵R⁶, —N(R⁵)C(═O)R⁶, —SR⁵, —S(═O)₂R⁵, —S(═O)₂OR⁵, —S(═O)₂NR⁵R⁶, cyano and —SiR⁵R⁶R⁷; wherein R⁵, R⁶, and R⁷ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl and [C₃-C₅]-cycloalkyl.
 12. A compound of formula (I) and (Ia) to (Id) according to claim 11 wherein. Z², Z³, Z⁴, Z⁵, Z⁶, Z⁷, Z⁸ and Z⁹ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, methyl, ethyl, iso-propyl, iso-butyl, tert-butyl, [C₁-C₄]-haloalkyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, methoxy, trifluoromethoxy, acetyl, trifluoroacetyl and cyano.
 13. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein K¹, K² and W¹ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, methyl, ethyl, iso-propyl, iso-butyl, tert-butyl, allyl, propargyl, cyclopropyl, acetyl, trifluoroacetyl and mesyl.
 14. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein Q is selected in the list consisting of Q¹ to Q²⁶.
 15. A compound of formula (I) and (Ia) to (Id) according to claim 14 wherein Q is selected in the list consisting of Q³, Q⁴, Q⁶, Q⁷, Q⁹, Q¹² and Q¹⁵.
 16. A compound of formula (I) and (Ia) to (Id) according to claim 1 wherein X¹ to X⁵ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, aryl, aryl-[C₁-C₂]-alkyl, —C(═O)R¹⁴, —C(═O)OR¹⁴, —C(═O)NR¹⁴R¹⁵, —CR¹⁴═NOR¹⁵, —CR¹⁴═N—NR¹⁵R¹⁶, —OR¹⁴, —OSiR¹⁴R¹⁵R¹⁶, —OC(═O)R⁴, —OC(═O)OR¹⁴, —OC(═O)NR¹⁴R¹⁵, —NR¹⁴R¹⁵, —N(R¹⁴)C(═O)R¹⁵, —SR¹⁴, —S(═O)₂R¹⁴, —S(═O)₂OR¹⁴, —S(═O)₂NR¹⁴R¹⁵, cyano and —SiR¹⁴R¹⁵R¹⁶; wherein R¹⁴, R¹⁵ and R¹⁶ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl and [C₃-C₅]-cycloalkyl, aryl and aryl-[C₁-C₂]-alkyl.
 17. A compound of formula (I) and (Ia) to (Id) according to claim 16 wherein X¹ to X⁵ are independently selected in the list consisting of hydrogen, halogen, [C₁-C₄]-alkyl, methyl, iso-propyl, iso-butyl, tert-butyl, [C₁-C₄]-haloalkyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, benzyl, phenethyl, methoxy, trifluoromethoxy, acetyl, trifluoroacetyl and cyano.
 18. A compound of formula (Ia) to (Id) according to claim 2 wherein E¹ is selected in the list consisting of [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl and cyclopropyl.
 19. A compound of formula (I) and (Ia) to (Id) according to claim 18 wherein E¹ is selected in the list consisting of methyl, ethyl, iso-propyl, allyl, propargyl, cyclopropyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NR¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹ and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of methyl and trifluoromethyl.
 20. A compound of formula (Ia) to (Id) according to claim 2 wherein E² is selected in the list consisting of halogen, [C₁-C₄]-alkyl, [C₁-C₄]-haloalkyl, [C₂-C₄]-alkenyl, [C₂-C₄]-haloalkenyl, [C₂-C₄]-alkynyl, [C₂-C₄]-haloalkynyl, [C₃-C₅]-cycloalkyl, [C₃-C₅]-halocycloalkyl, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸, —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)OR¹⁸, —OC(═O)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹, —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰, —N═CR¹⁸R¹⁹, —N═C—NR¹⁸R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹, —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)₂NR¹⁹R²⁰, —SR¹⁸, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹, cyano and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, [C₁-C₄]-alkyl and [C₁-C₄]-haloalkyl.
 21. A compound of formula (I) and (Ia) to (Id) according to claim 20 wherein E² is selected in the list consisting of methyl, ethyl, iso-propyl, trifluoromethyl, difluoromethyl, allyl, ethynyl, propargyl, cyclopropyl, cyano, —C(═O)R¹⁸, —C(═O)OR¹⁸, —C(═O)NR¹⁸R¹⁹, —CR¹⁸═NOR¹⁹, —CR¹⁸═N—NR¹⁹R²⁰, —OR¹⁸, —OSiR¹⁸R¹⁹R²⁰, —OC(═O)R¹⁸, —OC(═O)OR¹⁸, —OC(═O)NR¹⁸R¹⁹, —NR¹⁸R¹⁹, —N(R¹⁸)C(═O)R¹⁹, —N(R¹⁸)C(═O)OR¹⁹, —N(R¹⁸)C(═O)NR¹⁹R²⁰, —N(R¹⁸)C(═S)R¹⁹, —N(R¹⁸)C(═S)NR¹⁹R²⁰, —N═CR¹⁸R¹⁹, —N═C—NR¹⁸R¹⁹, —N(R¹⁸)S(═O)₂R¹⁹, —N(R¹⁸)S(═O)₂OR¹⁹, —N(R¹⁸)S(═O)₂NR¹⁹R²⁰, —SR¹⁸, —S(═O)₂R¹⁸, —S(═O)₂OR¹⁸, —S(═O)₂NR¹⁸R¹⁹ and —SiR¹⁸R¹⁹R²⁰; wherein R¹⁸, R¹⁹ and R²⁰ are independently selected in the list consisting of hydrogen, methyl and trifluoromethyl.
 23. The use of a compound of formula (I) or (Ia) to (Id) according to claim 1 for curatively or preventively controlling the phytopathogenic fungi of plants or crops.
 24. A method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or (Ia) to (Id) according to claim 1 is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
 25. The use of the fungicide composition of claim 22 for curatively or preventively controlling the phytopathogenic fungi of plants or crops.
 26. A method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterized in that a fungicide composition of claim 22 is applied to the seed, the plant, the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow. 